It is very easy to generate a custom report in MLS that will list members and their email address. You cannot use the email address as a filter criteria, but you can show the email address in the resulting custom report. Then it is a simple matter to group those with no email address, or move the data to a spreadsheet application and delete the rows with email addresses.
I have attached an instruction to build one such report in MLS. I also attached the .mls file that can be imported into anyone's MLS installation to generate this report (the .mls file contains no membership data - only the instructions to generate the report from the MLS database). MLS still can do some pretty cool custom reports, even though many membership clerks have largely abandoned it. We have over 150 custom reports in our MLS (though some have been rendered unnecessary due to Ward Council access to LCR).
Note: with custom reports, MLS does a poor job of managing the column widths. You should preview each custom report before printing and drag the columns wider or narrower to get the result you want. The MLS screen is not exactly WYSIWYG - you will probably have to do some via trial and error. When you get it how you like it, MLS will prompt you to save the column settings when you exit the report.